Stabilizing cellulosic textile materials against shrinkage employing glyoxal and a metal silicofluoride as a catalyst



Patented Sept. 5, 1950 STABILIZING CELLULOSIC TEXTILE MATE- RIALSAGAINST SHRINKAGE EMPLOYING GLYOXAL AND A METAL SILICOFLUORIDE AS ACATALYST Leo Beer, Providence, R. I.,.assignor to Alrose ChemicalCompany, Cranston, R. I., a corporation of Rhode Island No Drawing.Application October 14, 1948, Serial No. 54,581

9 Claims. (Cl. 8116.4)

This invention relates to the treatment of textile materials ofnaturalvor regenerated cellulose or mixtures thereof for the purpose ofeliminating their tendency to shrink upon washing in aqueous soapsolutions at elevated temperatures.

It also relates to the treatment of such designated textile materials tosecure excellent stability against laundry shrinkage without incurringany appreciable loss in tensile strength or abrasion resistance.

The normal fabrics made from these fibers and mixtures containing thesame, i. e. without treatment, have a marked yet normal tendency aftersuccessive washing and cleaning to shrink to different degrees; thisaffects the wearability of the fabric.

Many attempts have been made to develop and perfect processes whichcontrol the shrinkage of fabrics with and without the use of resins.Fabrics have been treated :by conventionally employed processes in theindustry with formaldehyde or compounds which split off formaldehyde,but always in the presence of strong acids, or in the presence of a saltwhich is acid-reacting per se or becomes acidic during processing, suchas baking at elevated temperatures. This results in deterioration intensile strength and abrasion which is especially serious in the case ofcotton.

By a more recent development, cellulosic fibers and fabrics have beentreated by a process characterized by the employment of glyoxal, andwherein oxalic acid is the catalyst to confer stability against laundryshrinkage. But whereas rayon fabrics are made shrinkproof to a greatdegree and the shrinkage tendency significantly curbed in the case ofcotton fabrics, the former displays a loss in the range of in tensilestrength, and the latter the range of 50%.

In the inventors copending U. S. patent application Serial Number722,955, filed January 18, 1947, which has become Patent 2,484,545, withissue date of October 11, 1949, this disadvantage is overcome byemploying a substantially neutral water-soluble alkali metal salt of anacid whose oxidation potential in solution of unit activity referred tothe normal hydrogen electrode at C. is greater than -0.9 volt, such asthe chlorate, nitrate of perchlorate, instead of oxalic acid. In hiscopending U. S. patent application, Serial 2 Number 750,159, filed May23, 1947, the use of an alkali metal sulfate to modify the catalyticaction of the oxalic acid is described.

Broadly, it is an object of .the present invention to secur theadvantage of employing a solution of glyoxal to render textilematerials, composed of natural cellulosic material or regeneratedcellulose, stable against shrinkage yet rfiitigating the attendantdisadvantages in loss of tensile strength and abrasion resistance inmost presently employed commercial processes.

It is the object of the present invention to treat textile materialsthat are formed predominantly of natural cellulosic materials orregenerated cellulose with dilute aqueous solutions of glyoxal in thepresence of a soluble inorganic salt of silicofluoric acid to stabilizethem against shrinkage, but with no appreciable loss in tensile strengthor abrasion resistance.

It is a more specific object of the present invention to securestabilization of the aforesaid types of textile materials againstshrinkage but without significantly impairing their tensile strength,wherein the fibers are wetted by a dilute solution of glyoxal andsubsequently baked at C. or higher until the desired shrinkage controlhas been secured i. e. a substantial reaction between the cellulose andglyoxal has taken place.

Other objects and features of the invention will be apparent from thefollowing description:

Broadly speaking, my invention consists in employing certain inorganicsalts of silicofluoric acid in catalyzing the glyoxal-cellulose reactionwhich must take place within the fibers of natural or regeneratedcellulose if shrinkage resistance is to be attained when using glyoxal.In my invention the acidity of the impregnated goods decreases duringbaking of the goods at temperatures of 100 C. and above. In terms of pHvalues this means an increase of the pH, contrary to known methods wherethe pH decreases during concentration and baking. Also whereas thepresence of oxalic acid increases the acidity of the aqueousimpregnating glyoxal solution, the presence of magnesium silicofluoridedecreases the acidity of the aqueous glyoxal impregnating solution,because an aqueous solution of this salt is not as acidic as the glyoxalsolution. Furthermore as explained below,'magnesium silicofluoridedecomposes during the baking step to yield a more basic reactingcomponent and a volatile acid component. The basic component which isformed on the cloth protects it, which would not be true in the case ofa fixed acid component.

By the present invention, any form of textile material of the typesdescribed infra is thoroughly wetted with the aqueous solution ofglyoxal in the presence of the silicofluoride, the excess liquid removedmechanically, the textile material then dried, and cured or baked at anelevated temperature until a substantial shrinkage reduction has beenachieved. This shrinkage reduction may be explained as due to a.reaction which is believed to have taken place in the fibers of thetextile material, 1. e. the glyoxalcellulose reaction The goods are thenscoured, rinsed, hydroextracted and dried without tension. Finally thefabrics are steamed and framed to predetermined finished dimensions (asindicated by a laundering test). It will be understood, however, thatthese steps subsequent to the baking do not form part of the presentinvention.

As has been pointed out supra cellulosic textile materials treated bythe present invention are characterized by permanent stability againstshrinkage. Glyoxal (also known as oxaldehyde or ethandial, and whosestructural formula is CHO.CHO) is the agent which reacts with thecellulose and is responsible for conferring these properties. Theinorganic salts of silicofluoric acid act as the catalyst to promote thereaction. Under the condition described herein glyoxal without-thecaltalyst will not confer these properties.

While it appears that all metal salts of silicofiuoric acid are suitablefor use as catalysts, the water-solubility and hydrolysis rate imposesome limitations on the selection of the salts of this group from anoperating standpoint. Since it is generally desired that the color ofthe treated material should remain unchanged this makes certain of thesesalts undesirable.

The sodium-, and potassium-, and ammonium silicofluorides have eachproven satisfactory but are dimcult to handle because of their lowsolubility in water and aqueous solutions. The armmonium saltsfurthermore tend to yellow the fabric on curing.

Zinc-, magnesium-. and cadmium salts are suitable, and because they arehighly water-sole uble and do not have the secondary characteristic ofdiscolorln the cellulosic fabrics, either natural or regenerated, theyare the choice. In general, I prefer to use magnesium silicofluoride,commercially avialable as MgSiF'aGHzO, because of its ready solubilityand its stability at moderate temperatures. That last expression will beunderstood to embrace the ranges up through 150 C. and somewhat aboveunder the conditions of operation herein.

Moreover, I should like to point out that other metal salts ofsilicofluoric acid, such as nickel-, cobalt-, iron-, manganese-, ormercury are highly water-soluble and could be used if discolorationcaused by the metallic ion is not objectionable for the ultimatepurpose. In fact, it is possible by the use of these latter compounds toobtain simultaneously shrinkage control and mildew-resistance orrotproofing, and in some cases even water repellencey, or flameproofing;this can be efiected by precipitating the metallic salt by a suitableafter-treatment, i. e. after baking, using alkali, soap, alkaliphosphates or other basic chemical agents.

A possible explantation of the action of these 4 compounds on curing,which is the stage of the process when the glyoxal-cellulose reactiontakes place, is the decomposition of the silicofluoride as follows:

The volatile silicon fluoride acts as the reaction catalyst while thesomewhat alkaline magnesium fluoride, which is formed directly on thecloth, acts as a buffer or protective agent for the cloth. It is thoughtthat this is what transpires that makes it possible to carry out thereaction without loss in tensile strength or abrasion resistance.

In the aqueous wetting solution the suggested range for concentration ofglyoxal is 1% to 10% inclusive of glyoxal, preferably 1% to 5%inclusive, based upon the weight of the treating solution, When thequantity is less the goods treated by this process lacks significantshrinkage resistance. When the quantity exceeds 10% there is the risk ofdamage to the fabric, depending somewhat on the baking temperature andtime. Technical glyoxal is sold as 30% by weight glyoxal, so the amounton the 100% basis will have to be computed. As to the catalyst, theamount of about 0.3% to 3.0% by weight or the aqueous impregnatingsolution, but preferably 0.5% to 2.0% inclusive, in terms of MgSlFaGHzO,is the suggested range. The above percentages of concentration ofglyoxal and the silicofiuoride catalyst are each based upon a 100% pickup of liquid in reference to the weight of the goods.

Fabrics or fibers of regenerated and/or natural cellulose display littleor no tendency to shrink upon washing after treatment according to thepresent invention. The method herein disclosed can moreover besuccessfully applied to mixtures of natural and regenerated cellulose aswell as to either alone, or to mixtures containing either regeneratedcellulose or natural cellulose with cellulose acetate, provided thefabric does not contain more than 50% cellulose acetate. The last may bereplaced by other cellulose esters or organic acids, such as thepropionate. B the term regenerated cellulose I mean viscose orcuprammonium rayon or saponified cellulose acetate, By the term naturalcellulose I means such fibers as cotton, linen, hemp and jute, moreparticularly cotton. The textile materials coming within the preview ofthis invention are those composed of or predominantly of cellulosefibers of natural vegetative origin or of regenerated cellulose.

The treatment by this invention, and which is described in more detailbelow, may be employed on fabrics containing any percentage of cottonsince the treatment has no deleterious eflect on natural cellulosefiber. This process is thus an extremely important improvement over theknown aldehyde processes for shrinkproofing fibers of vegetable origin.

The regenerated and/or natural cellulose may be treated in any form, bywhich is meant filaments, fibers, staple or yarn; woven, knitted,braided or pretreated fabrics as well as clothing or other finishedgoods. And the term textile material unless otherwise qualified includesthese.

The step of impregnating the fibers or filaments with the aqueoussolution of glyoxal and silicofluoride may take place at any timesubsequent to any desizing of the fabric which is to be treated. But alltraces of starch, gums, glue or natural resin and other sizing agentsshould be removed for optimum results in order to permit the aqueoussolution to penetrate the fibrous or filament material and enter theheart of the fibers.

The impregnation or wetting of the textile material with the aqueousliquid or solution can be accomplished in any desired manner, such as byimmersion. spraying or coating'by other modes. Usually this is done in acontinuous manner, the amount applied being governed by the rate oftravel of the textile material. The excess liquid should be removedbefore the drying step. This may be achieved by various mechanical meanssuch as squeeze rolls, centrifugal devices or vacuum extractors. Thisallows a pick-up of a predetermined percentage, such as 100% liquidretention on the dry basis of the goods.

The drying and curing can, alternatively, be

carried out as a single operation. But it is preferred to make two stepsof this, and the description will be explained more fully as to thatmode. The drying is carried out at low temper atures such as IO-100 C.and preferably at 100 C. although it could be at even lowertemperatures, and until the moisture contact has been reduced to about10%; this moisture limit is not exactly critical but the fabric shouldnot be overdry. For woven fabrics, this step is accomplished on a tenterframe.

The cellulosic textile material thus treated is then baked orcuredusuall in a loop dryer without tension. While temperatures of 100C. or just slightly above can be used, because of the element of time, arange of 130 C. to 150 C. with an inverse time interval of 6 to 2minutes is preferred. It is of course essential that the time intervalin this baking step be of sufficient duration that the treated textilematerial when subjected to the Federal CCC-T-191A test exhibits asubstantial reduction in shrinkage in comparison to the untreated sampleof the same material. Those temperature-time conditions giving theoptimum stability against shrinkage wlil normally be selected. Selectionand choice for optimum results is not confined to this step but isequally applicable to the conditions in each of the steps and theprocess as a whole however.

After the curing or baking step the textile material is washed withouttension, dried, and finally framed to the dimensions indicated in apreliminary wash test. In same cases, overfeed devices in the finaltentering operation are employed, but in other cases, it is necessary toapply some warpwise batching tension to counteract supercontraction inthe previous drying operation. However the steps outlined in thisparagraph are not part of the present invention, al-

though they are supplemental operations before the textile material isput into industrial channels or trade.

If desired the hand" or body of the goods treated can be modified in thedirection of either softness or a stiffer finish at will by theintroduction to the impregnation bath of suitable agents, such as cationsofteners for the former effect, or such vegetable or animal colloids asstarches, gums, glues, gelatins and modified starches for the lattereffect. But the process of this invention is carried out in the absenceof any phenolic or amidic compounds capable of forming resinous bodieswith aldehydes under the conditions employed. Therefore, fabrics treatedby my method show no tendency toward chlorine retention.

Fabrics of the natural cellulosic type or of the vresult in somehydrolysis).

regenerated type treated by my invention herein are stabilized againstshrinkage upon washing in aqueous solutions at elevated temperatures aspointed out supra. The superior nature of this process can beappreciated when, moreover, it is realized that this obtained effect isa permanent one, and even successive washings at the boil do not affectthe results. Fabrics of viscose or cuprammonium yarns so processed arefurther improved as borne out by the fact that they show less tendencyto fuzz during washing, as compared to an untreated material similarlywashed. The loss in tensile strength after this treatment is negligible,and no diminutlon of abrasion resistance occurs. Provided that the dyesused on the fabrics are fast to repeated boiling in aqueous soapsolutions, the treated materials can be considered boil-fast withrespect to shrinkage control and. wearing properties.

This invention will be more clearly understood by reference to thefollowing examples. It is to be understood, however, that these examplesare merely illustrative of the process, and that the invention is notlimited thereto but rather is defined in the appended claims. In theexamples the term check has the meaning of untreated or original. Theterm total shrinkage signifies the entire shrinkage occurring to thematerial (in either warp or filling direction) due to complete sequenceof processing and wash testing, or wash testing alone in the case ofuntreated or check sample. The term compression shrinkage" signifies thetotal shrinkage of an untreated or unprocessed materialafter thesecuring and wash testing. The term gain over compression shrinkagesignifies the advantage in length (or width) gained by use of thedescribed process over that of a swatch which has not been subjected tothe process, i. e. after both have been scoured and wash tested.

EXAMPLE 1 spun viscose rayon fabric treated The impregnating solutionshad the following compositions:

Solutions Components No. A No. B

Glyoxal, 30 per cent technical "grams" MgSiFdEhO do a Han The magnesiumsilicofiuoride was dissolved in water at about 38 C. (highertemperatures might A. wetting agent may advantageously be added to theserespective baths to reduce the time necessary for complete saturation,as was'done in this example.

Two samples of the above fabric were impregnated on a padder with theabove solutions No. A and No. B respectively. Each of them was thensqueezed to a liquor retention of 100%, based on the weight of drygoods, and then dried without tension at about 100 C. Care was exercisedto avoid over-drying (8% to 10% moisture should remain in the goods atthis point).

After drying, the samples were each divided into two parts (A-l, A-2 and3-4. 3-2) and cured as follows:

A-1 and B-1 6 minutes at 138 C. A-2 and B-2 6 minutes at 127 C.

7 The samples were thereupon washed, rinsed and dried. They were thenlaundered together with the check sample by the accelerated l-hour washtest described in Federal Specification CCC-T-191A. The followingshrinkages were observed based upon the measurements:

Warp shrinkage (in percentages) Gainover Sam 1 Ida tifleati Traded@1312: T

a n on an s on p ured age Shrinkage Measured from scoured dimensions. 1Measured from original dimensions.

The samples were subjected to tensile strength measurements. the valueswhich were:

Tensile strength (lbs. grab-test) Dry Wet Check 40 A-l.-. 4s 1s s-1 4a1a A-2. 46 15 13-2. 43 15 Conclusions A considerable degree of permanentstabilization against shrinkage was obtained (see gain over compressiveshrinkage" column) without any loss in tensile strength.

EXAMPLE 2 100% spun rayon fabric treated The impregnating solutions hadthe following compositions:

Components No. 1 No. 2

Glyoxal 3 tech grams MgSiF .ilH% d Water. to?

The two solutions were made up, the samples of the fabric (designatedNo. l and No. 2 respectively) wetted with the above solutionsrespectively, squeezed to 100% retention and dried at about 100 C. as inExample 1. They were 8 Warp tensile strength, pounds Check 54 #1 (after3rd wash) 59 #2 (after 3rd wash) 53 Conclusion Again, excellentpermanency against shrinkage was obtained, with no appreciable loss inThe two solutions were made up, the samples of the fabric immersedtherein, squeezed to 100% retention and dried at about 100 C., similarto Example 1. They were then baked for 2 minutes at 150 C., the sametemperature as in Example 2. They were then washed and dried as in thencured for 3 /2 minutes at 150 C. They were then rinsed, scoured anddried and tested as in Example 1. In this case, laundering shrinkage wasmeasured from the scoured dimensions.

Warp shrinkage (in percentage) Successive 1 hr. Sample Treated washes 1Total 23 32? Ideatifl- Bclznd d Shrm lp sion on n ure age 0 1st 2nd 3rdShrinkage Cheek 7.5 l.4 4.2 -ll.7 N0. 1 3. 9 0. 7 0. 6 0 3. 9 7. 8 N0. 23. 3 +0. 6 o. 6 0 3. 3 8. 4

1 Measured irom scoured dimensions. I Measured irom original dimensions.

Example 1.

War shrinkage, per cent Successive Gain Over Sample Identi- Tmatedl'hour wash I Total Compresfication 2:? g? sion 15; 2nd Shrinkage 1Measured from scoured dimensions. 1 Measured lrom original dimensions.

The samples were then subjected to tensile strength measurements.

Tensile strength (lbs., grab-test) Check 54 #1 49 #2 44 ConclusionsCotton was also permanently stabilized considerably, using asilicofluoride catalyst, with only slight loss of strength. This is inmarked contrast with losses of about 50% when oxalic is used as in theprior art under the same conditions as herein.

EXAMPLE 4 Spun viscose rayon fabric treated The wetting solution had thefollowing composition: 70 gms. of glyoxal (30% tech.), 15 gms. magnesiumsilicofiuoride (MgSiFs'6H20) and 0.2 gm. Igepal CTA extra (:1 commercialpolyethylene condensation product manufactured by General DyestuffCorporation of New York city) per liter of water.

Three difierent types of spun viscose rayon fabrics designated QualityA, Quality B and Quality C, were impregnated with this solution,squeezed to pick-up of solution and dried as in Example 1. They werethen baked for 3 minutes at C.

The samples were then washed, rinsed, scoured I and dried as in Example2.

Warp shrinkage, percent 10 mentioned. In this case laundry shrinkage wasmeasured from treated dimensions.

Warp shrinkage, per cent Successive 1 hr. Gain over Sam Successive l-hr.washes Gain Over plo 'lotal m s plc e agg washes 'gg g cogi i a msg gi-Shrinkgg f en ca on m 2nd m shrinkage lst 2d 3d 4th 5th f ShrinkageCheck -5.s -5.s -1.a -7.4 -s.o s.o Quality #1 0.4 -o.1 +0.6 -0.6 --0.67.4 check -11.4 #2 -1.5 0.6 -1.1 -1.1 6.9 Quality A,

treated -s.1 0 +0.5 0 -3.1 as Quality B, Measuredfrom scoureddimensions. qchplprt B l2. 2 Measured from scoured dimensions.

118 y m r in l- -e.4 +0.6 +0.1 +0.1 -s.1 0.5 From the above examples, itwill be seen that g L Y by employing the silicofluoride catalysts whichI Quality 0, have described, I have succeeded in obtaining rayon andcotton fabrics stabilized against laun- 1 M med H m mm d dim Signs 1 dryshrinkage, without appreciable diminution in Mgsmd g original dlmgsionsz29 the tensile strength or abrasion resistance ofthe Qualities A and Cwere then subjected to both tensile strength and abrasion resistancemeasurements, the value of which were:

Conclusions It is quite apparent that the spun viscose rayon fabricshave been quite satisfactorily rendered permanently stable againstprogressive shrinkage, while the tensile strength and abrasionresistance has not been lessened. 0

EXAMPLE 5 Spun rayon fabric treated The impregnating solution had thefollowing composition: '70 gms. of 30% tech. glyoxal, 10 gms.

of sodium silicofluoride per liter of water.

A sample of the above fabric was impregnated with this solution at 40C., squeezed to 100% pick-up of solution and dried as in Example 1.

It was then baked at 300 C. for 3 minutes.

It was then washed, rinsed, scoured and dried as in the previousExamples 1 to 4, its tensile strength measured as in those examples orin its abrasion resistance as in Example 4.

EXAMPLE6 100% 'spun rayon fabric treated The impregnating solutions hadthe following compositions:

Quanti- Quanti- Components ties ties Glyoxal 307 tech grams- MgSiFabHzOdo 15 ZnSiFaGHzO dn Igepal C-TA 510.-.- 0.5 0.5 Water htcrs 1 1 Thesamples of the above fabric -(designated #1 and #2 respectively) wereimpregnated with 70 the above solutions respectively which had been madeup as in Ex. 1. They were then squeezed and dried as in Ex. 1. They werethen cured at 150 C. for 3% minutes. This was followed by the rinsing,scouring and washing steps a previously fabric. 0n the other hand,baking such fabrics which have been impregnated with an aqueous solutionof oxalic acid and glyoxal of 1.0-2.5 pI-I \and containing thecorresponding quantity of 25 glyoxal per volume, followed by squeezingand drying wherein the treating conditions correspond in each, result insevere damage to cotton such as aloss of 30-60% in tensile strength oreven more; and it frequently reduces the tensile strength of rayon by asmuch as 10 to 25%. This deleterious effect is described further in my U.S. Patent #2,484,545 of October 11, 1949, and my copending U. S. Patentapplication Ser. No. 750,159, filed May 23, 1947.

Because high temperatures in forming the solu tions and in the wettingstep may cause partial hydrolysis of the metallic silicofluoride suchtemperatures should be avoided. Because an excess of glyoxal and also ofthe silicofluoride are harmful to' cellulosic fibers, the minimumquantity of each which will produce the desired shrinkage reductionwithout decrease in tensile strength should be used, taking into accountthe time and temperature.

In the claims the term "short chain aliphatic aci embraces those notabove four carbon atoms. I

It will be realized by those skilled in the art that changes may be madein the process hereinbefore described without departing from the scopeof the claims.

Having described my invention, what I claim and desire to secure byLetters Patent protection is:

1. In the process of stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials of the group consisting of natural cellulose,regenerated cellulose, and mixtures with each other and up tosubstantially 50% of cellulose esters of a short chain aliphatic organicacid, with an aqueous liquid containing substantially 1.0 to 10.0%glyoxal and a water-soluble metallic silicofluoride in an amount of atleast substantially 0.3%, each by weight, on the basis of the treatingsolution and a 100% pick-up based on the dry weight of the goods,mechanically removing surplus impregnating liquid, then drying thetextile material after said liquid removal, and curing it at atemperature above substantially 100 C. for a period of time inverselyrelated to the temperature until there is a substantial reduction inshrinkage in comparison with the un-treated textile material.

2. In the process oi stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials of the group consisting of natural cellulose,regenerated cellulose and mixtures with each other and up tosubstantially 50% of cellulose esters of a short chain aliphatic organicacid, with an aqueous liquid containing substantially 1.0 to 10.0%glyoxal and a highly water-soluble metallic silicofiuoride in amount ofsubstantially 0.3-3.0%, each by weight, on the basis of the treatingsolution and a 100% pick-up based on the dry weight of the goods.mechanically removing surplus impregnatin liquid, then drying thetextile material after said liquid removal, and curing it at atemperature between 100 C. and 150 C. substantially, for 'a period oftime inversely related to the temperature until there is a substantialreduction in shrinkage in comparison with the untreated textilematerial.

3. In the prooem of stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials of the group consisting 01' natural cellulose,regenerated cellulose and mixtures with each other and up tosubstantially 50% of cellulose acetate, with an aqueous solutioncontaining substantially 1.0% to 10.0% glyoxal and 0.3% to 3.0% oi.magnesium silicofluoride each by weight, on the basis of the treatingsolution, and a 100% pick-up based on the dry weight 01' the goods,mechanically removing surplus impregnating liquid, then drying thetextile material after said liquid removal, and curing it at atemperature between 100 C. and 150 C. substantially, for a period 01time inversely related to the temperature until there is a substantialreduction in shrinkage in comparison with the untreated textilematerial.

4. In the process of stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials of the group consisting of natural cellulose,regenerated cellulose and mixtures with each other and up tosubstantially 50% of cellulose acetate, with an aqueous solutioncontaining substantially 1.0% to 3.0 of glyoxal and 0.5% to 1.5% ofmagnesium silicofluoride each by weight, on the basis of thetreatingsolution and a 100% pick-up based on the dry weight of the goods,mechanically removing surplus impregnating liquid then drying thetextile material after said liquid removal, and

up based on the dry weight of the goods, me-

chanically removing surplus impregnating liquid,

curing it at between 130 and 150 C. substan tially, for substantially 2minutes to 6 minutes, the time being inversely related to thetemperaure.

5. In the process of stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials of the group consisting of natural cellulose,regenerated cellulose and mixtures with each other and up tosubstantially 50% of cellulose esters of a short chain aliphatic organicacid, with an aqueous liquid containing substantially 1.0 to 10.0%glyoxal and a silicofluoride of a member of group IIB of the periodictable (magnesium group) in amount of substantially 0.3-3.0%, each byweight, on the basis of the treating solution and a 100% pickthen dryingthe textile material after said liquid removal, and curing it at atemperature between C. and C. substantially, for a period of timeinversely related to the temperature until there is a substantialreduction in shrinkage in comparison with the untreated textilematerial.

6. In the process of stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials oi the group consisting of natural cellulose,regenerated cellulose and mixtures with each other and up tosubstantially 50% of cellulose acetate, with an aqueous solutioncontaining substantially 1.0% to 10.0% glyoxal and 0.3% to 3.0% of asilicofluoride of a member of group 1128. of the periodic table(magnesium group) each by weight, on the basis of the treating solutionand a 100% pick-up based on the dry weight of the goods, mechanicallyremoving surplus impregnating liquid, then drying the textile materialafter said liquid removal, and curing it at a temperature between 100 C,and 150? C. substantially, for a period of time inversely related to thetemperature until there is a substantial reduction in shrinkage incomparison with the untreated textile material.

'7. In the process of stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials of the group consistin of natural cellulose,regenerated cellulose and mixtures with each other and up tosubstantially 50% of cellulose esters of a short chain aliphatic organicacid, with an aqueous solution containing substantially 1.0 to 10.0%glyoxal and a silicoiluoride of a member of group VIII of the periodictable (iron group) in amount of substantially 0.3-3.0% each by weight,on the basis of the treating solution and a 100% pick-up based on thedry weight of the goods, mechanically removing surplus impregnatingliquid, then drying the textile material after said liquid removal, andcuring it at a temperature betweenv 100 C, and 150 C. substantially, fora period of time inversely related to the temperature until there is asubstantial reduction in shrinkage in comparison with the untreatedtextile material.

8. In the process of stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials of the group consisting of natural cellulose,regenerated cellulose and mixtures with each other and up tosubstantially 50% of cellulose acetate, with an aqueous solutioncontaining substantially 1.0 to 10.0% glyoxal and 03-30% of asilicofluoride of a member of group VIII of the periodic table (irongroup) each by weight, on the basis of the treating solution and a 100%pick-up based onthe dry weight of the goods, mechanically removingsurplus impegnating liquid, then drying the textile material after saidliquid removal, and ouring it at a temperature between 100 C. and 150 C,substantially, for a period of time inversely related to the temperatureuntil there is a substantial reduction in shrinkage in comparison withthe untreated textile material.

9. In the process of stabilizing a textile material against shrinkageupon washing in hot aqueous solutions without significant loss intensile strength and abrasion resistance, the steps of impregnatingtextile materials of the group consisting of natural cellulose,regenerated cellulose and mixtures with each other and up tosubstantially 50% of cellulose esters of a short chain aliphatic organicacid, with an aqueous liquid containing substantially 1.0 to 10.0%glyoxal and manganese siiicofluoride in amount of substantiaily 0.3-3.0%each by weight, on the basis of the treating solution and a 100% pick-upbased on the dry weight of the goods, mechanically removing surplusimpregnating liquid, then drying the textile material after said liquidremoval, and curing it at a temperature between 100 and 150 C.substantially, for a period of time in- 15 versely related to thetemperature until there is a substantial reduction in shrinkage incomparison with the untreated textile material,

- LEO BEER.

aarnaancas men The following references are of record in the file ofthis patent: 1

l4 UNITED STATES PATENTS Number Name Date 1,016,928 Bishop Feb. 13, 19121,483,519 Phair Feb. 12, 1924 1,514,067 Phair NOV. 4, 1924 2,233,402Cresswell Mar. 4, 1941 2,412,832 Pfefler Dec. 17, 1946 2,436,076 PfeflerFeb. 17, 1948 FOREIGN PATENTS Number Country Date 585,679 Great BritainRb, 19, 1947 OTHER REFERENCES Rayon Textile Monthly for August 1946. mes51 (405) and 52 (408)

1. IN THE PROCESS OF STABILIZING A TEXTILE MATERIAL AGAINST SHRINKAGEUPON WASHING IN HOT AQUEOUS SOLUTIONS WITHOUD SIGNIFICANT LOSS INTENSILE STRENGTH AND ABRASION RESISTANCE, THE STEPS OF IMPREGNATINGTEXTILE MATERIALS OF THE GROUP CONSISTING OF NATURAL CELLULOSE,REGENERATED CELLULOSE, AND MIXTURES WITH EACH OTHER AND UP TOSUBSTANTIALLY 50% OF CELLULOSE ESTERS OF A SHORT CHAIN ALIPHATIC ORGANICACID, WITH AN AQUEOUS LIQUID CONTAINING SUBSTANTIALLY 1.0 TO 10.0%GLYOXAL AND A WATER-SOLUBLE METALLIC SILICOFLUORIDE IN AN AMOUNT OF ATLEAST SUBSTANTIALLY 0.3%, EACH BY WEIGHT, ON THE BASIS OF THE TREATINGSOLUTION AND A 100% PICK-UP BASED ON THE DRY WEIGHT OF THE GOODS,MECHANICALLY REMOVING SURPLUS IMPREGNATING LIQUID, THEN DRYING THETEXTILE MATERIAL AFTER SAID LIQUID REMOVAL, AND CURING IT AT ATEMPERATURE ABOVE SUBSTANTIALLY 100*C. FOR A PERIOD OF TIME INVERSELYRELATED TO THE TEMPERATURE UNTIL THERE IS A SUBSTANTIAL REDUCTION INSHRINKAGE IN COMPARISON WITH THE UN-TREATED TEXTILE MATERIAL.